CN101267989A

CN101267989A - Bottles made from metallocene polypropylene for delivery of fragrances

Info

Publication number: CN101267989A
Application number: CNA2006800342958A
Authority: CN
Inventors: J·S·特伦特; F·J·兰德尔; T·M·科瓦拉; J·J·伦克尔
Original assignee: SC Johnson and Son Inc
Current assignee: SC Johnson and Son Inc
Priority date: 2005-08-16
Filing date: 2006-08-16
Publication date: 2008-09-17
Anticipated expiration: 2026-08-16
Also published as: EP1934099B1; US7416766B2; AU2006279629B2; ES2363031T3; KR101013739B1; MX2008002182A; AU2006279629A1; CA2618917A1; BRPI0614282A2; CN101267989B; EP1934099A1; ATE510775T1; US20070042149A1; KR20080046636A; WO2007022168A1

Abstract

Bottles made of metallocene polypropylene (mPP) for storage and dispensing reservoirs for fragrance compositions, in particular fragrance oils, are described. The mPP bottles can be used in warmer units for slow release dispensing of the fragrance therein. The metallocene polypropylene bottles can be produced by extrusion or injection blow molding, injection molding, injection stretch blow molding (single or two stage), or other suitable molding process. The mPP bottles may optionally have at least one barrier coating layer and/or adhering layer. The mPP bottles may optionally be fluorinated. The mPP bottles have good clarity and possess the required physical properties needed when the bottles are filled on a production line.

Description

The bottle of making by metallocene polypropylene that is used for delivery of fragrances

Technical field

The present invention relates to by metallocene polypropylene (mPP) make as the storage that contains flavor compositions (especially fragrance (fragrance oil)) and distribute the bottle of reservoir.Bottle of the present invention especially is suitable for the distribution device that slowly-releasing distributes spices, especially electronic or battery powered warmer.

Background technology

The flexible cell of the blow molding of being made by metallocene polypropylene, ducted body, film, coating and the sheet material of injection mo(u)lding are known in the art.The perfume container of being made by polypropylene also is known.

For example, the U.S. Patent Application Publication that Winckels arranged well known in the prior art 2003/0209566A1 number, it discloses the packaging product that is used for gel or emulsifiable paste cosmetics.This packaging product have flexible cell or jar and the stiff case that holds jar.Flexible cell can be the polypropylene that obtains by metallocene catalysis.Rigid construction can be a thermoplastic material, as polypropylene.

The also known U.S. Patent Application Publication that Winckels arranged is 2003/0183639A1 number in the prior art, and it discloses the multi-part deformable container that is used for gel or emulsifiable paste cosmetic product, and wherein the deformable component of this container can be made by metallocene polypropylene.

The also known US Patent the 6th, 645 that people such as Eckstein are arranged in the prior art, 641B2 number, it discloses the polymeric material that is used to make packaging structure such as film, sheet material, bottle cap material, pouch, pipe and sack.This structure can be the single or multiple lift structure.The available single site catalysts of these layers (as metallocene) catalyzing propone and making.The dispense container of this patent disclosure is removable (collapsible).

The also known U.S. Patent Application Publication that Winckels arranged is 2005/0045668A1 number in the prior art, and it discloses the jar that is used to pack gel or emulsifiable paste cosmetic product.This jar design has two dispensing orifices.When product has pasty consistency and during not with flow by gravity, preferably this jar comprises at least one elastomeric deformable wall.Deformable wall can be by the polyolefin that is obtained by metallocene catalysis, and for example metallocene polypropylene is made.

The also known US Patent the 6th, 786 that people such as Schram are arranged of prior art, 427B2 number, it discloses interchangeable liquid vessel, and this liquid vessel contains the liquid that will disperse in atomising device.This liquid vessel can be by duroplasts, as the molded bottle that forms of polypropylene.

The also known US Patent the 6th, 537 that people such as Grasmeder are arranged of prior art, 478B1 number, it discloses the acrylic polymers that metallocene catalysis obtains that passes through that uses in the various goods of injection mo(u)lding.

Prior art is also known U.S. Patent Application Publication 2004/0152842A1 number of Dunaway, and it discloses the polyolefin blend compositions and by its product of making, for example bottle of blow molding.This polymer blend composition comprises the low density polyethylene (LDPE) that polypropylene and metallocene generate.Polypropylene can use any appropriate catalyst, and for example Ziegler-Natta or metallocene catalyst adopt the polymerization technique of any routine to produce.The example of the blow-molded container made from polymer composition is Detergent bottle, Sofe drink bottle, jar and accumulator drum.Other goods that produce comprise film, coating and flexible packaging.

Prior art is also known U.S. Patent Application Publication 2004/0094468A1 number of Fritze, and it discloses freeze resistant water filter.Cartridge structure is by rigid polyolefin polymers, makes as polypropylene.But it is frangible that these poly-mers can become in freezing range.Filter seat is by the bigger polyolefin polymer of elasticity, makes as metallocene polypropylene.

Prior art is also known people's such as Gurumus U.S. Patent Application Publication 2002/0077394A1 number, and it discloses and has contained the polyacrylic composite that is prepared from through metallocene catalyst and specific hindered amine as light stabilizer system polymerization.

Prior art is also known US Patent the 5th, 591, No. 395, the 5th, 647, No. 053, the 5th, 903, No. 710, the 5th, 909, No. 845, the 5th, 976, No. 503 and the 6th, 123, No. 935, they disclose air freshener, except the patent of ' 395, they each device all disclosed container or seat can make by polypropylene.

Prior art is also known US Patent the 4th, 314, and No. 915, the 4th, 411, No. 829 and the 4th, 434, No. 306, they disclose the fragrance composite.

Prior art is also known US Patent the 6th, 727,332B2 number, U.S. Patent Application Publication 2004/0044106A1 number and european patent application 1422249A1 number, 0537130A1 number, 1169356B1 number and 1189985B1 number, they disclose the preparation of metallocene polypropylene.

Summary of the invention

The present invention relates to by metallocene polypropylene (mPP) make as the storage that contains flavor compositions (especially fragrance) and distribute the bottle of reservoir.The mPP bottle especially is suitable for the distribution device that slowly-releasing distributes spices, especially electronic or battery powered warmer.

More particularly, preferred implementation of the present invention relates to the bottle of being made by mPP that can preserve fragrance, this bottle is inserted in the distribution device, and preferably with power supply bonded assembly warmer, power supply is for example wall power sockets, automobile power source jack, battery or analogue.MPP bottle of the present invention is used in particular for holding the composite that comprises fragrance, causes leaking because fragrance can penetrate in many polymer architectures and destroy poly-mer, this means losing and might damaging contiguous material around of product.Bottle of the present invention has rigid construction.The present invention relates to use the acrylic resin of metallocene single site catalyst production.By convention, acrylic resin is produced by the many site catalysts of Ziegler-Natta.The mPP bottle produces by blow molding, injection mo(u)lding or any other suitable moulding technology.The mPP bottle can randomly have one deck barrier coat and/or bonding coat at least.One or more layers barrier coat can be in the inside and/or the outside of bottle, and this bottle is interpreted as and comprises inner and outer wall.

Metallocene polypropylene rigid bottles has shown beat all good result in weight loss tests, and has good visibility, and has required physical property when being full of bottle on manufacturing line.

Can understand these and other aspects of the present invention, feature and advantage better with relevant description with reference to the accompanying drawings, in these accompanying drawings and associated description, illustrate and described preferred implementation of the present invention.

Description of drawings

With reference to the accompanying drawings:

Fig. 1 has shown the effect of bottle plastics to spices (Mandarin) loss rate.

Fig. 2 has shown the loss in weight result of the spices in the various polypropylene vial (HawaiianBreeze) under different temperatures.

Fig. 3 has shown in the time of 50 ℃ the effect to Hawaiian Breeze spices loss in weight of bottle that different plastics make.

Fig. 4 has shown the effect to Mandarin spices loss in weight under different condition of in the time of 50 ℃ various bottles.

Fig. 5 has shown the lateral plan of the embodiment of bottle of the present invention, has core to exist in this bottle.

Fig. 6 has shown the front elevation of the embodiment of bottle of the present invention.

Fig. 7 has shown the bottle of being made by the mPP resin of the present invention, this bottle inside and outside barrier coat is arranged all.

Fig. 8 schematically illustrates the cross-sectional plane of bottle of the present invention, and this bottle has bonding coat between bottle material and barrier coat.

The specific embodiment

The present invention relates to by metallocene polypropylene (mPP) make as the storage that contains flavor compositions (especially fragrance) and distribute the bottle of reservoir.Contain flavor compositions and be used to surrounding environment that fragrance is provided, but can contain one or more other composition, as carrier (for example, water, alcohol or analogue) or active component (for example, bactericidal agent is as triethylene glycol (TEG) or analogue).The present invention relates to the mPP bottle of preserving fragrance especially.The long term storage of fragrance and distribute problem takes place especially easily because fragrance can be immersed in the poly-mer of preserving bottle, and destroys poly-mer and causes leaking.Owing to can lose product and damage circumferential surface or material, leakage must be deletrious.Bottle of the present invention has rigid construction, and is particularly useful for the distribution device that slowly-releasing distributes spices.The present invention relates to use the acrylic resin of metallocene single site catalyst generation.By convention, acrylic resin is produced by the many site catalysts of Ziegler-Natta.Further described so, the mPP bottle is to form by traditional blow molding, injection mo(u)lding or any other suitable manner.The mPP bottle can randomly have one deck barrier coat and/or bonding coat at least.

As described below, found unexpectedly that mPP resin bottle of the present invention provides good preservation for fragrance, and use by being inserted in the warm distribution device, with provide slowly-releasing to distribute after suitable power supply such as wall power sockets, battery or analogue are connected.But the mPP bottle can be used for needs and prolongs other rigid container purposes that spices is preserved.In order to discuss and with regard to the following specific embodiment that proposes, this paper will be that example further describes the mPP bottle to preserve and to distribute fragrance.

With regard to regard to the storage and distribution reservoir of fragrance, as the good result of weight loss tests, its good visibility with when this bottle has required physical property when being filled on the manufacturing line as shown in, mPP bottle of the present invention provides beyond thought advantage.These products of detailed hereafter and characteristic.

The mPP resin of being made by metallocene single site catalyst replaces traditional acrylic resin of being made by the many site catalysts of Ziegler-Natta (ZNPP), can be used to effectively be manufactured on store and divide timing to preserve the rigid bottles of fragrance.By the alternative present fragrance of the bottle bottle that the mPP resin is made, the latter is made by more expensive resin, as

210 and 218, they are acrylonitrile (AN)-methyl acrylate (MA) copolymers that are grafted on the government rubber, and are sold by Innovene (subsidiary company of BP Chemicals).

Metallocene polypropylene resins is made by many suppliers, and these suppliers comprise DowChemical, ExxonMobil, Basell and Total Petrochemicals USA, Inc..The mPP that is produced by Total has desired molecule amount and melt flows as detailed below, so it is particularly suitable for automated production.In preferred embodiment, for example, the mPP bottle uses by TotalPetrochemicals USA by injection blow molding moulding (IBM) technology and/or extrusion and blow molding (EBM) technology, and the Total M3282MZ resin manufacture that Inc. makes forms.These mPP bottle performances in weight loss tests are unexpectedly good, has good visibility, and when on manufacturing line, being full of bottle, has a required physical property (, top load intensity, modulus in flexure intensity and impact resistance) with the fragrance that spices arranged.

Metallocene polypropylene resins generally has very narrow molecular weight distribution, and the level of extractable matter is very low.The mol wt of mPP resin is measured by the melt flows of this resin usually.More particularly, when the mol wt of mPP resin increased or reduces, the melt flows of mPP resin changed.Specifically, when the mol wt of mPP resin increased, the melt flows of mPP resin reduced, and vice versa.In preferred implementation of the present invention, for EBM technology, the melt flows of mPP resin be about 1 the gram/10 minutes to about 10 the gram/10 minutes, for IBM technology be about 1 the gram/10 minutes to about 40 the gram/10 minutes.But, for all types of blow molding technologies, the melt flows of mPP resin of the present invention can be about 0.5 the gram/10 minutes to about 50 the gram/10 minutes, more preferably about 1 the gram/10 minutes to about 30 the gram/10 minutes, and most preferably about 1 the gram/10 minutes to about 20 the gram/10 minutes.

MPP resin bottle of the present invention can be made by blow molding, injection mo(u)lding or any other suitable molding process (that is, single phase or two stages are annotated stretch blow moulding (ISBM) technology).For extrusion and blow molding, the melt flows of preferred mPP resin is that about 0.5 gram restrained/10 minutes in/10 minutes extremely about 5.For the injection blow molding moulding, the melt flows of preferred mPP resin is that about 1 gram restrained/10 minutes in/10 minutes extremely about 20, thinks that the mPP resin provides the required intensity and the barrier property of enhancing.With regard to performance, also provide in test identical data result no matter take which kind of method of moulding, mPP bottle of the present invention all to have identical desirable characteristics.The molding process of any routine can be used to make mPP resin bottle of the present invention so that required result to be provided.

In manufacturing process, routinely clarifier or nucleating agent are added in the polypropylene,, add visibility and rigidity that clarifier or nucleating agent have increased resin because polypropylene was muddy originally.Clarifier or nucleating agent preferably are added in the poly-mer with very little amount, and the polyacrylic crystalline rate that change is increased, thereby the crystal structure that is called as spherocrystal that makes formation is littler and more than the polypropylene of nucleation not.Because spherulite size reduces, scattering of light reduces when light passes through this material, so visibility improves.

MPP with clarification as described below is used for test to show advantage of the present invention, because maker adds clarifier at present, and does not provide the commercially available mPP resin made from nucleating agent that is in the target flowing scope of melt.But if necessary, can use does not have the mPP of clarifier or nucleating agent resin, and this can provide identical object intensity and barrier properties result, but the visibility that has is very poor.

In the preferred embodiment of the present invention, the mPP resin bottle is made separately by mPP.The result shows, uses mPP just can provide enough barrier properties in these bottles separately.But in another embodiment, for example, as shown in Fig. 7 and 8, bottle can randomly have barrier coat as the coating on bottle inwall and/or the outer wall, so that improve barrier properties under the situation that needs ES because of special perfume oil properties.The barrier properties of these enhancings comprises having in the use/storage temperature more than 50 ℃, prevent that spices/composite from appearing bottle, anti-block penetrates to bottle and reduce water and enter in the bottle from atmosphere.

Compare with mPP resin of the present invention, other resins also can provide good barrier properties, as

Resin, but it is very expensive.When being used to preserve fragrance, because spices and/or oxygen penetrable material or cause the rapid decline (that is, environmental stress cracking problem) of physical property, some resin also has other shortcoming/problem.

In another embodiment, the mPP resin bottle can have film on the bottle wall, as bonding coat, so that barrier coat is combined on the mPP bottle.The mPP bottle of the present invention that has or do not have barrier coat can both provide the barrier properties of enhancing.Therefore, the preferred implementation of mPP bottle of the present invention does not have barrier coat on the inwall of mPP bottle or outer wall.After this manner, do not use special application step to be coated with barrier coat and just can make the mPP bottle, this application step relates to the use of solvent and removing of solvent.But the mPP bottle can randomly have barrier coat, has or do not have bonding coat.

Therefore, mPP resin bottle of the present invention provides the barrier properties that strengthens, as prevents that therefore seeing through also of product from preventing product losses, and anti-block penetrates in the bottle, otherwise may cause the improper oxidation of some perfume composition, or prevent because water penetrates the weight that causes to the bottle increases.The barrier properties of other enhancings of mPP bottle comprises that good visibility and these bottles are used for the predetermined physical properties of delivery of fragrance oils.These predetermined physical propertys include but not limited to higher top load intensity, modulus in flexure intensity and impact resistance.

The mPP bottle also can be fluoridized, as passing through the contact fluorine gas.Fluorination has improved the barrier properties that prevents fragrance.But fluorination can not reduce seeing through of oxygen significantly.Further describe fluorination below in conjunction with embodiment.

The various components of the mPP resin bottle of being mentioned among the top embodiment that describe in detail and given below are presented in the table 1.Table 1 comprises the type and the function of various components (chemical name and adopted name/trademark) and percentage by weight, every kind of composition.

Table 1

The following examples are to want casehistory the present invention and unrestricted the present invention.

The following describes when contacting the unexpected performance difference between mPP and the ZNPP poly-mer with the oily spices of general use.

Embodiment 1-is as shown in the swell test, and metallocene homopolymer and Zeigler-Natta polypropylene random copolymer are to the chemical resistance of fragrance composition relatively.

Two types poly-in the sample of weighing of alkene (1) Total M3282MZ (the mPP resin of clarification) and (2) Total NO3112-2 (the Ziegler-Natta polypropylene random copolymer of NA21 nucleation below is designated as ZN-RCPP) place the bottle that contains 40 kinds of fragrance component samples that generally are used for preparing various fragrance.Two kinds of acrylic resins are all by Total Petrochemicals USA, and Inc. provides.All samples places in the environmental chamber, 85 (29.4 ℃) following two weeks, takes out then, and paper towel dried is also weighed.The increase of calculated weight, the result is presented in the table 2.

After showing 2-@85 2 weeks of submergence, the percentum that polypropylene specimen weight increases: mPP and ZNPP

		M3282MZ		ZN-RCPP
		M3282MZ		ZN-RCPP		Sample	Fragrance component	The % swellbility	Remarks	The % swellbility	Remarks
1	Aldehyde MNA	1.27％		5.74％		Sample	Fragrance component	The % swellbility	Remarks	The % swellbility	Remarks
1	Aldehyde MNA	1.27％		5.74％		2	The fluffy ester of lattice	1.37％		3.19％
3	Applinal (ethyl 2-(2-methyl isophthalic acid, 3-dioxolanes-2-ester) ethanol)	0.62％		1.41％		2	The fluffy ester of lattice	1.37％		3.19％
3		0.62％		1.41％		4	Superfine benzyl acetate	1.92％		2.57％
5	Benzylalcohol	0.60％		0.50％		4	Superfine benzyl acetate	1.92％		2.57％
5	Benzylalcohol	0.60％		0.50％		6	Benzyl propionate	2.59％		3.53％
7	White camphor	5.04％	Warpage	14.52％	Warpage	6	Benzyl propionate	2.59％		3.53％
7	White camphor	5.04％	Warpage	14.52％	Warpage	8	Carbitol	0.62％		0.60％
9	Cineole	1.37％		15.29％	Warpage	8	Carbitol	0.62％		0.60％
9	Cineole	1.37％		15.29％	Warpage	10	Citronellol (Citrolellol)	0.56％		0.79％

11	Clove leaf oil	1.31％		2.32％
11	Clove leaf oil	1.31％		2.32％		12	Cyclamen aldehyde	0.88％		2.07％
13	Diethyl malonate	1.22％		0.92％		12	Cyclamen aldehyde	0.88％		2.07％
13	Diethyl malonate	1.22％		0.92％		14	Dihydromyrcenol	5.27％		0.77％
15	DowDPM	0.78％		0.78％		14	Dihydromyrcenol	5.27％		0.77％
15	DowDPM	0.78％		0.78％		16	Eucalyptus oil	2.02％		14.02％	Warpage
17	Refining eugenol (Eugeneol)	0.86％		1.83％		16	Eucalyptus oil	2.02％		14.02％	Warpage
17	Refining eugenol (Eugeneol)	0.86％		1.83％		18	Tricyclo decenyl propionate (florocyclene)	1.53％		4.47％	Warpage
19	Geraniol	0.69％		0.36％		18	Tricyclo decenyl propionate (florocyclene)	1.53％		4.47％	Warpage
19	Geraniol	0.69％		0.36％		20	Geranyl acetate	2.03％		4.64％
21	Grape-fruit seed oil	12.07％		12.55％	Warpage	20	Geranyl acetate	2.03％		4.64％
21	Grape-fruit seed oil	12.07％		12.55％	Warpage	22	Hexyl acetate	7.78％		6.75％	Warpage
23	Jasminolene	1.14％		1.43％		22	Hexyl acetate	7.78％		6.75％	Warpage
23	Jasminolene	1.14％		1.43％		24	Isobornyl acetate	0.87％		2.31％
25	Fragrant kindness (jasmacylene)	1.36％		3.84％	Warpage	24	Isobornyl acetate	0.87％		2.31％
25	Fragrant kindness (jasmacylene)	1.36％		3.84％	Warpage	26	Lavandin oil	0.99％		2.05％
27	Lavender oil	1.23％		3.57％	Warpage	26	Lavandin oil	0.99％		2.05％
27	Lavender oil	1.23％		3.57％	Warpage	28	Ligustral	2.27％		8.02％
29	Lilial	0.61％		1.06％		28	Ligustral	2.27％		8.02％
29	Lilial	0.61％		1.06％		30	Linalool	0.69％		1.68％
31	Bergamio	0.75％		2.36％		30	Linalool	0.69％		1.68％
31	Bergamio	0.75％		2.36％		32	Orange Florida	12.00％	Warpage	13.42％	Warpage
33	Oranger terpene	10.94％	Warpage	13.72％	Warpage	32	Orange Florida	12.00％	Warpage	13.42％	Warpage
33	Oranger terpene	10.94％	Warpage	13.72％	Warpage	34	Verdox (Ortholate)	0.48％		1.94％
35	Peppermint oil	1.04％		6.02％	Warpage	34	Verdox (Ortholate)	0.48％		1.94％
35	Peppermint oil	1.04％		6.02％	Warpage	36	Phenylethyl alcohol	0.52％		0.13％
37	PTBCHA	1.04％		3.32％	Warpage	36	Phenylethyl alcohol	0.52％		0.13％
37	PTBCHA	1.04％		3.32％	Warpage	38	The α terpilenol	0.92％		1.16％
39	Terpinyl acetate	1.28％		3.04％	Warpage	38	The α terpilenol	0.92％		1.16％
39	Terpinyl acetate	1.28％		3.04％	Warpage	40	Allyl heptanoate	6.63％		7.05％

As shown in table 2, the weight increase that M3282MZ mPP resin is produced is starkly lower than the ZN-RCPP resin generally.Table 2 also shows the physical deformation where polypropylene specimen has taken place.For grape-fruit seed oil, oranger terpene and Orange Florida, two types of polypropylene specimen are all observed and are surpassed 10% weight increase.Grape-fruit seed oil, oranger terpene and Orange Florida contain high-caliber D-citrene (shaddock 90%, oranger terpene 94%), and the D-citrene is soluble in polypropylene.In addition, the ZN-RCPP sample contacts with eucalyptus oil also to observe with white camphor, cineole and surpasses 10% weight increase.Camphor is the solid that melts down at 175 ℃, and white camphor oil contains cineole, camphor, borneol, amphene, menthol, borneol, sobrerone and cinene.Cinene is being identical with citrene chemically, and difference is that it contains D and L optical isomer simultaneously.Therefore, swelling may be caused by cinene and sobrerone content.Eucalyptus oil has about 70-80% cineole, but also contains amphene, citronellal, fenchene and phellandrene.Because cineole and eucalyptus oil energy swells polypropylene, so cineole may be the reagent that causes swelling.

Therefore, as if the most of fragrance components in the table 2 can not cause the remarkable swelling of the sample that mPP makes.Exception is the fragrance that contains high levels of limonene.Cineole, may also have cinene and sobrerone all is the problem place.Therefore, when needs used polypropylene vial, spices should not contain a large amount of fragrance component types that can be dissolved in the polypropylene, or alternatively, will (multilayer) barrier coat be coated on bottle and went up a barrier properties with the raising bottle.The chemical results of many fragrance components is as follows in the table 2.Following chemical constitution numbering is corresponding with the sample number into spectrum of fragrance component in the table 2.

Embodiment 2-is as shown in the weight loss tests, and metallocene homopolymer and Zeigler-Natta random copolymers are to the chemical resistance of Mandarin fragrance relatively.

Mandarin spices contains about 30% citrene, because leakage and the high spices migration problem relevant with bottle, it no longer is contained in the ZN-RCPP bottle in market sale by Changing Paradigms.Therefore, select this spices, because its invasive character can move by polypropylene, and how different the proof metallocene polypropylene resins compares with Ziegler-Natta catalyzed random copolymer acrylic resin (the commercial resin that is used for making apothecary jar).Table 3 shown when 25 gram Mandarin spices by ZN-CRPP, mPP and

Preserve the loss in weight result after 113 days in the apothecary jar that 210 resins (being grafted on the acrylonitrile methyl acrylate copolymer on the government rubber) are made.

The 210th, be used to preserve fragrance at present and use various kinds of electric warmer units to distribute this oily material.ZN-RCPP is the random copolymers that contains about 5% ethylene comonomer content.MPP is the metallocene homopolymer of commodity Total M3282MZ resin by name.In addition, some mPP bottles of making are fluoridized to be become as three kinds of the Fluoro-SealInternational defined different levels (promptly, level 3, level 5 and over one's competence 5), can detect like this to determine whether can reduce penetrating of more solubility fragrance components effectively both surface modifications of mPP bottle inner and outer wall, above-mentioned solubility fragrance component such as citrene, white camphor, Orange Florida, oranger terpene and allyl heptanoate (see Table 2, wherein these fragrance components cause the buckling deformation of mPP sample).These samples by Fluoro-Seal International by the mPP bottle being contacted with fluorine gas and being fluoridized.Although fluorination has improved the barrier properties to fragrance, fluorination can not reduce seeing through of oxygen.

The loss in weight of table 3-Mandarin spices in various bottles relatively

Monitoring is sealed in nearly four months of the loss in weight of Mandarin spices under three kinds of different temperatures in the apothecary jar that is equipped with wick and lid.2 week back loss in weightes become constant, find repeatable fine between the repeated trial.With regard to regard to the preferred selection of present perfume oil bottle, as expectation,

The unit is all lower than the loss speed of any one polypropylene units.But,

Therefore 210 resins are very expensive, are starved of the material product as an alternative with suitable characteristic.The result of table 3 shows that clearly the mPP bottle provides the loss speed lower than the ZN-RCPP bottle.In addition, the fluorination of mPP bottle makes the loss speed of Mandarin spices be reduced to lower degree.For example, this effect to loss speed is presented among Fig. 1, and this figure illustrates the effect of bottle plastics to Mandarin perfume loss speed.Therefore, might reach with the combination of modification being carried out on the surface by fluorination by using the mPP resin to make apothecary jar The performance of bottle.

Embodiment 3-is as shown in the weight loss tests, and metallocene polypropylene and Zeigler-Natta polypropylene random copolymer are to the chemical resistance of Hawaiian Breeze fragrance relatively.

Use by Total Petrochemicals USA by Monarch Plastics Limited, Inc. Total M3282MZ that provides (mPP of clarification) and Total M3132-2 (the Ziegler-Natta polypropylene random copolymer of NA21 nucleation, later on and be labeled as " hPP " in Fig. 2) resin is made 1 ounce of polypropylene vial of thin-walled by extrusion and blow molding (EBM) technology.In these bottles, add the HawaiianBreeze spices that 40 grams are made by Takasago International Corporation.The sensed sealing of all bottles that are full of afterwards, closely capping, and weigh, be exposed to temperature 23EC (73.4), 53 ℃ (127.4) and 63EC (145.4) then.Carried out loss in weight and measure in 91 days, the result is shown among Fig. 2.When exposing at room temperature (23EC), two types polypropylene vial is all held Hawaiian Breeze spices.By with temperature increase to 53EC and 63EC, can more clearly see the performance difference between metallocene and the Ziegler-Natta polypropylene.After 91 days, the HawaiianBreeze loss in weight in the hPP bottle for 2 times of the loss seen in the mPP bottle, is 1.7 times under 63EC under 53EC.

Embodiment 4-strengthens the chemical resistance of metallocene polypropylene bottles to Hawaiian Breeze and Mandarin fragrance by dip coated.

The preparation dipping solution:

To three kinds of different weight percent levels 3%, 7% and 10%, annotate respectively is solution A, B and C to 210 resin dissolves in Dimethyl fomamide (DMF).In addition, the Eastman of preparation 1.6wt% ^TMThe solution (solution D) of adhesion promoter 550-1 in dimethylbenzene like this will be effectively attached on the mPP surface by the coating of solution A, B and C coating with modification mPP bottle surface (inside and outside).

Dip coated technology: first step of bottle coating process is that the mPP bottle is immersed in the solution D that is heated to 50EC, be emptied completely the solution in the bottle, and make it at first air drying 1 hour, then in being set in the vacuum drying chamber of 55EC dry 1 hour to finish drying process.The mPP bottle of the solution D coating of each group drying is immersed among solution A, B and the C individually then, and wherein every kind of solution was heated to 95EC before soaking.In case bottle is immersed among solution A, B or the C, with they emptying solution, air drying 1 hour, in being set in the vacuum drying chamber of 55EC dry 12-20 hour then.Then bottle is full of Hawaiian Breeze and Mandarin fragrance, is adjusted to 50EC and carries out weight loss tests.Be full of

Bottle and not coating the mPP bottle in contrast, and with from solution A, B and C

The mPP bottle of coating is compared.

Weight loss tests result: Fig. 3 and 4 has shown

The mPP bottle of coating be full of Hawaiian Breeze and Mandarin fragrance respectively

Bottle and not the mPP bottle of coating compare loss in weight result after 45 days (every kind of condition following two detect bottle).Fig. 3 and 4 all shown barrier layer as The application of 210 resins can reduce the transmitance of fragrance by mPP bottle wall effectively very significantly.Increase barrier coat thickness by soaking casting 3% to 7% to 10% solution, reduced loss in weight progressively, reached 100%

The weight loss values of the bottle that 210 resins are made.

Embodiment 5-is as shown in the weight loss tests, and metallocene polypropylene is to the chemical resistance of various fragrance.

Not the mPP of coating and

Bottle has been full of the fragrance that 6 kinds of Takasago InternationalCorporation and Quest Internation make, so that at room temperature study loss in weight over time.Table 4 has shown that in fact these fragrance do not have loss in weight in 6 months time, because water vapour migrates into weight increase on the contrary in the bottle.With regard to water intake, the mPP bottle is better than Bottle.

Table 4: the sealing mPP with

Bottle is compared 6 months loss in weight/increase test at ambient temperature

MPP bottle of the present invention can be used the pigmented tinting of different amounts, thereby the colored bottle of various tones is provided or can also therefore have color without pigment.

Be used in an embodiment making that the mPP resin of bottle preferably as above described in detail by TotalPetrochemicals USA, the Total Polypropylene M3282MZ that Inc. makes.M3282MZ has following properties: melt flow index is 2.3 grams/10 minutes; Density is 0.905 grams per milliliter; Fusing point is 307EF (153EC); Tensile strength is 4,900psi (33.8MPa); Stretch ratio is 72%; With modulus in flexure be 216,000psi (1,490MPa).

Metallocene homopolymer can preferably be used with the following flowing scope of melt that is as above described in detail: 0.5 to 50 gram/10 minutes, more preferably 1 to 30 gram is/10 minutes, and most preferably 1 to 20 restrains/10 minutes.When the intensity of bottle is not considered to important parameter, can use the metallocene polypropylene copolymer of the identical flowing scope of melt of the flowing scope of melt that provided with metallocene homopolymer.

Fig. 5 and 6 has shown the preferred implementation of the bottle made from the mPP resin.Bottle preferably has the bottle of bottleneck.Bottle can be any suitable shape, and preferably is fit to the receiving portion of kinds of electric warmer units, and this warmer will be used for distributing the fragrance in the bottle.Shown in the imaginary line among Fig. 5, the tube core that has cuff is inserted in the bottleneck of bottle.The case description that wherein can be used for the kinds of electric warmer units of mPP bottle of the present invention is the US Patent the 5th of " vapor distribution device (Vapor Dispensing Device) " at exercise question, 647, No. 053 is the US Patent the 5th of " the wick-based emission of liquid system (Wick-Based Liquid EmanationSystem With Child-Resistant Overcap) that has anti-children's top cover " with exercise question, 909, in No. 845, two pieces of patents are incorporated herein by reference.A kind of such warmer is S.C.Johnson﹠amp; Son, Inc., the name that Racine, Wisconsin produce is called

The commercial goods.

Fig. 7 has shown the bottle of being made by the mPP resin, on this bottle inside and outside barrier coat is arranged all.As above describe in detail, barrier coat also can only be coated on the inside or the outside of bottle.Suitable barrier coating comprises

Polyacrylinitrile (PAN), nylon 6, nylon 6-6, Vingon (PVDC), polyvinylchloride (PVC), PEN (PEN), polyethylene terephthalate of being sold by Eastman (PET) or copolyesters (being called glucosylation (glucolised) polyethylene terephthalate) are (PETG), glucosylation poly terephthalic acid hexamethylene dimethyl ester (glucolised polycyclohexylenedimethylene terephthalate) (PCTG) or pentachloro-THIOANISOLE (PCTA), or can be as the effective barrier coat or the minimizing oxygen of fragrance, any material of carbon dioxide or aqueous vapor migration.

Fig. 8 has shown the scheme drawing of bottle cross-sectional plane of the present invention, and it has shown between bottle material and the barrier coating that as above described in detail and has used bonding coat.As an example, the bottle among Fig. 8 is mPP, and bonding coat is Eastman ^TMAdhesion promotor 550-1, barrier coat is

210 or polyacrylinitrile (PAN).

Although the present invention quite at length is described, those skilled in the art will recognize that the present invention can implement in the mode outside the described embodiment, described embodiment is illustrative purposes and unrestricted as an example only.Therefore, the scope of claims should not be limited to the description to embodiment described herein.

Claims

1. bottle that is used to preserve and distribute flavor compositions, it comprises the bottle of being made up of metallocene polypropylene.

2. bottle according to claim 1, it further comprises the die material that forms the bottleneck of one and be arranged in described bottleneck with described bottle, and described die material comprises to small part and is positioned at the first of described bottle and from the outward extending second portion of described bottle.

3. bottle according to claim 1, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 50 from about 0.5 gram.

4. bottle according to claim 2, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 50 from about 0.5 gram.

5. bottle according to claim 1, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 40 from about 0.5 gram.

6. bottle according to claim 2, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 40 from about 0.5 gram.

7. bottle according to claim 1, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 20 from about 1 gram.

8. bottle according to claim 2, the flowing scope of melt of wherein said metallocene polypropylene are to restrain/10 minutes in/10 minutes extremely about 20 from about 1 gram.

9. bottle according to claim 1, it further is included in the inside face of described bottle and/or the barrier coat on the outside face.

10. bottle according to claim 2, it further is included in the inside face of described bottle and/or the barrier coat on the outside face.

11. bottle according to claim 9, wherein said barrier coat comprises following at least a: be grafted on acrylonitrile-methyl acrylate copolymer, polyacrylinitrile, nylon 6, nylon 6-6, Vingon, polyvinylchloride, PEN, polyethylene terephthalate, glucosylation polyethylene terephthalate, glucosylation poly terephthalic acid hexamethylene dimethyl ester or pentachloro-THIOANISOLE on the government rubber.

12. bottle according to claim 10, wherein said barrier coat comprises following at least a: be grafted on acrylonitrile-methyl acrylate copolymer, polyacrylinitrile, nylon 6, nylon 6-6, Vingon, polyvinylchloride, PEN, polyethylene terephthalate, glucosylation polyethylene terephthalate, glucosylation poly terephthalic acid hexamethylene dimethyl ester or pentachloro-THIOANISOLE on the government rubber.

13. bottle according to claim 9, it further is included in the bonding coat between described barrier coat and the described bottle.

14. bottle according to claim 10, it further is included in the bonding coat between described barrier coat and the described bottle.

15. bottle according to claim 1, wherein said metallocene polypropylene is fluoridized.

16. bottle according to claim 2, wherein said metallocene polypropylene is fluoridized.